Ruthenium (II) Complexes Bearing Heteroleptic Terpyridine Ligands: Synthesis, Photophysics and Solar Energy Conversion

Abstract

Abstract Heteroleptic ruthenium (II) complexes featuring donor functionalized phenyl‐terpyridine (ph‐tpy) and a monocarboxylic‐(ph‐tpy)/(tpy) are synthesized and characterized. Reactions of ruthenium (II) precursors at 80 °C favored heteroleptic complexes formation over the homoleptic side products. Visible light excitation of these complexes resulted in the metal‐to‐ligand charge transfer (MLCT) transitions. The inter‐planar torsional angle between the atoms of donor functionalized phenyl ring and the central pyridine (py) of the tpy core strongly influences visible light absorption and photovoltaic properties. The lower inter‐ring py‐ph torsion in the acceptor end of the MLCT structures and its increase in the oxidized doublets could prevent the back electron transfer. The ruthenium atom and the acceptor functionalized tpy host the triplet‐MLCT spin density. Ambient temperature excited‐state decay followed the energy gap law and occurred in the order of a few nanoseconds. Herein, we evaluate the photosensitizing ability of these complexes via a combined experimental and computational approach.